Use of wax mixtures for coatings

ABSTRACT

The invention provides for the use of mixtures of waxes which comprise 
     a) a homopolymer or copolymer of C 2 -C 18  α-olefins, prepared by means of metallocene catalysis, 
     and, as auxiliaries, one or more other waxes selected from the group consisting of 
     b) PE waxes, 
     c) PTFE waxes, 
     d) PP waxes, 
     e) amide waxes, 
     f) FT paraffins, 
     g) montan waxes, 
     h) natural waxes, 
     i) macrocrystalline and microcrystalline paraffins, 
     j) polar polyolefin waxes, or 
     k) sorbitan esters 
     for improving the properties of coating materials.

This application is a 371 of PCT/EP01/04778 filed Apr. 27, 2001.

The present invention relates to the use of metallocene waxes, their oxidates and blends thereof with further waxes, and also the corresponding micronisates, for coating materials.

In the preparation of coating materials, waxes are generally added in a concentration of 0.01-10%. The waxes in question are PE waxes, PTFE waxes, PP waxes, amide waxes, FT paraffins, montan waxes, natural waxes, macrocrystalline and microcrystalline paraffins, polyethylene copolymers, sorbitan esters and metallocene waxes, and also blends thereof, as disclosed in EP-A-0 890 619. The blends may be present in different combinations, both as powder mixtures and as melt mixtures.

These waxes are added in the form of flakes, granules, powders, dispersions, emulsions or micronisates, the preferred use form being regardable as a finely micronized powder with particle sizes up to 4 μm in DV₅₀ value. (DV₅₀ value: 50% of the wax particles are smaller than or equal to 4 μm). These waxes are used in order to achieve the following effects in the coating materials:

better scratch resistance

better abrasion resistance

better dispersing of pigments

better pigment stability

improvement in sedimentation tendency

improvement in redispersion of pigments

active orienting substance for effect pigments

effective flatting

satisfactory feel

improvement in lubricity

improvement in metal marking

achieving effective incorporation of effect pigments

influencing of rheological properties

better blocking resistance

better sandability

degassing additive in powder coatings

additive for increasing throughput in powder coatings.

These wax additives can be used in all coating systems (e.g., low solids, medium solids, high solids, solvent-based coating materials, aqueous or water-dilutable coating materials, powder coating materials, physically drying coating systems, chemically curing coating materials, and radiation-curing coating materials, such as UV coating materials, for example).

Since pure polyethylene waxes and metallocene waxes cannot be used in all coating systems, especially not in aqueous systems, use is also made of wax oxidates.

Since the individual types of wax display different effects in the coating materials, it is preferred to use wax mixtures of PE waxes, PTFE waxes, PP waxes, amide waxes, FT paraffins, montan waxes, natural waxes, macrocrystalline and microcrystalline paraffins, polyethylene copolymers, sorbitan esters and metallocene waxes in order to combine the abovementioned effects with one another and to obtain corresponding improvements in coating materials.

It was an object of the invention to find wax mixtures, for use in coating materials, which exhibit a particularly large number of the effects set out above. Surprisingly, the mixtures with metallocene waxes showed the most marked improvements. With these mixtures, a particular improvement is obtained in the grindability for the production of wax micronisates; in other words, the yields are increased.

A further advantage of using waxes produced by the metallocene process is their ready grindability, for which reason fewer auxiliaries are consumed in this case than in the case of wax mixtures comprising waxes produced, for example, with the Ziegler-Natta process.

The invention provides for the use of mixtures of waxes which comprise

a) a homopolymer or copolymer of C₂-C₁₈ α-olefins, prepared by means of metallocene catalysis, and also degradation waxes produced from relatively high-chain-length polyolefins produced by means of metallocene catalysis, and, as auxiliaries, one or more other waxes selected from the group consisting of

b) PE waxes,

c) PTFE waxes,

d) PP waxes,

e) amide waxes,

f) FT paraffins,

g) montan waxes,

h) natural waxes,

i) macrocrystalline and microcrystalline paraffins,

j) polar polyolefin waxes, or

k) sorbitan esters,

l) polyamides,

m) polyolefins,

n) PTFE,

o) wetting agents,

p) silicates

for improving the properties of coating materials.

The invention further provides coating materials comprising the wax mixtures described.

The homopolymer or copolymer of C₂-C₁₈ α-olefins prepared by means of metallocene catalysis (a) preferably have the following properties:

Dropping point (Dp): 80-165° C. Acid number (AN): 0-50 mg KOH/g Density: 0.87-1.03 g/cm³ Melt viscosity at 170° C.: 10-100 000 mPas.

Suitable polyolefin waxes include homopolymers of ethylene or propylene or copolymers of ethylene or propylene with one another or with one or more 1-olefins. 1-Olefins used include linear or branched olefins having 4-18 carbon atoms, preferably 4-6 carbon atoms. These olefins may have an aromatic substitution which is in conjugation with the olefinic double bond. Examples of such compounds are 1-butene, 1-hexene, 1-octene or 1-octadecene, and also styrene. Preference is given to copolymers of ethylene with propene or 1-butene. Ethylene copolymers of this kind have ethylene contents of 70-99.9% by weight, preferably 80-99% by weight.

Especially suitable polyolefin waxes are those having a dropping point of between 90 and 160° C., preferably between 100 and 155° C., a melt viscosity at 140° C. of between 10 and 10 000 mPas, preferably between 50 and 5 000 mPas, and a density at 20° C. of between 0.89 and 0.96 g/cm³, preferably between 0.91 and 0.94 g/cm³.

Also suitable are metallocene waxes modified by oxidation, such as may be obtained, for example, by treating the wax melt with air in accordance with EP-A-0 896 591. The disclosure content of this document in respect of the oxidative treatment of wax melts is hereby incorporated into the present specification by reference.

Metallocene catalysts for preparing the polyolefin waxes are chiral or nonchiral transition metal compounds of the formula M¹L_(x). The transition metal compound M¹L_(x) contains at least one central metal atom M¹ to which at least one π ligand, e.g., a cyclopentadienyl ligand, is attached. Furthermore, substituents, such as halogen, alkyl, alkoxy or aryl groups, for example, may be attached to the central metal atom M¹. M¹ is preferably an element from main group III, IV, V or VI of the periodic table of the elements, such as Ti, Zr or Hf. Cyclopentadienyl ligand comprehends unsubstituted cyclopentadienyl radicals and substituted cyclopentadienyl radicals such as methylcyclopentadienyl, indenyl, 2-methylindenyl, 2-methyl-4-phenylindenyl, tetrahydroindenyl or octahydrofluorenyl radicals. The π ligands may be bridged or non-bridged, with both single and multiple bridges—including bridges via ring systems—being possible. The metallocene designation also embraces compounds having more than one metallocene fragment, known as polynuclear metallocenes. These may have arbitrary substitution patterns and bridging variants. The individual metallocene fragments of such polynuclear metallocenes may be both identical to one another and different from one another. Examples of such polynuclear metallocenes are described, for example, in EP-A-0 632 063. Examples of general structural formulae of metallocenes and also of their activation with a cocatalyst are given, inter alia, in EP-A-0 571 882. The disclosure contents of these subjects in the two documents is hereby incorporated by reference.

Additive b) comprises, in preferred embodiments, polyethylene homopolymer and copolymer waxes which have not been prepared by means of metallocene catalysis and which have a number-average molecular weight of from 700 to 10 000 g/mol with a dropping point of between 80 and 140° C.

Additive c) comprises in preferred embodiments polytetrafluoroethylene having a molecular weight of between 30 000 and 2 000 000 g/mol, in particular between 100 000 and 1 000 000 g/mol.

Additive d) comprises, in preferred embodiments, polypropylene homopolymer and copolymer waxes which have not been prepared by means of metallocene catalysis and which have a number-average molecular weight of from 700 to 10 000 g/mol with a dropping point of between 80 and 160° C.

Additive e) comprises, in preferred embodiments, amide waxes preparable by reacting ammonia or ethylenediamine with saturated and/or unsaturated fatty acids. The fatty acids comprise, for example, stearic acid, tallow fatty acid, palmitic acid or erucic acid.

Additive f) comprises, in preferred embodiments, FT paraffins having a number-average molecular weight of from 400 to 800 g/mol with a dropping point from 80 to 125° C.

Additive g) preferably comprises montan waxes, including acid waxes and ester waxes having a carboxylic acid carbon chain length of from C₂₂ to C₃₆.

The ester waxes preferably comprise reaction products of the montanic acids with monohydric or polyhydric alcohols having 2 to 6 carbon atoms, such as ethanediol, butane-1,3-diol or propane-1,2,3-triol, for example.

Additive h) in one preferred embodiment comprises carnauba wax or candelilla wax.

Additive i) comprises paraffins and microcrystalline waxes which are obtained in the course of petroleum refining. The dropping points of such paraffins are preferably between 45 and 65° C., those of microcrystalline waxes of this kind preferably between 73 and 100° C.

Additive j) comprises, in preferred embodiments, polar polyolefin waxes preparable by oxidizing ethylene or propylene homopolymer and copolymer waxes or grafting them with maleic anhydride. Particularly preferred starting material for this purpose comprises polyolefin waxes having a dropping point of between 90 and 165° C., in particular between 100 and 160° C., a melt viscosity at 140° C. (polyethylene waxes) or at 170° C. (polypropylene waxes) of between 10 and 10000 mPas, in particular between 50 and 5000 mPas, and a density at 20° C. of between 0.85 and 0.96 g/cm³.

Additive k) comprises, in preferred embodiments, reaction products of sorbitol with saturated and/or unsaturated fatty acids and/or montanic acids. The fatty acids comprise, for example, stearic acid, tallow fatty acid, palmitic acid or erucic acid.

Additive l) preferably comprises ground polyamides, examples being polyamide-6, polyamide-6,6 or polyamide-12. The particle size of the polyamides is preferably in a range of 5-200 μm, in particular 10-100 μm.

Additive m) comprises polyolefins, i.e., for example, polypropylene, polyethylene or copolymers of propylene and ethylene of high or low density with molar weights of preferably from 10 000 to 1 000 000 D, in particular from 15 000 to 500 000 D, as numerical averages of the molecular weight, whose particle size as a result of grinding is in the range of preferably 5-200 μm, in particular 10-100 μm.

Additive n) comprises thermoplastic PTFE having a molar weight of preferably 500 000-10 000 000 D, in particular 500 000-2 000 000 D, as numerical average, whose particle size as a result of grinding is in the range of preferably 5-200 μm, in particular 10-100 μm.

Additive o) comprises amphiphilic compounds which generally lower the surface tension of liquids. The wetting agents comprise, for example, alkyl ethoxylates, fatty alcohol ethoxylates, alkylbenzenesulfonates or betaines.

Additive p) comprises silicates which are not used as filler or pigment in the formulas. It is preferred to use silicas or talc.

The proportion of ingredient a) to ingredients b) to p) may be varied in the range from 1 to 99% by weight a) to 1 to 99% by weight b) to p). Where a mixture of two or more of ingredients b) to p) is used, the indicated amount applies to the sum of the amounts of these ingredients.

In one preferred embodiment, the waxes are used in micronized form for the purpose according to the invention. Particular preference is given to the use of polyolefin wax and optionally admixed auxiliaries and additives as an ultrafine powder with a particle size distribution d₉₀<40 μm.

Parameters improved include the flatting of the coating materials, the dispersibility and stability (sedimentation tendency or bodying tendency) in coating materials and dispersions, an improvement in the slip, hardness and abrasion resistance, an increase in the throughput and improvement in pigment dispersion in powder coating materials, and better antiblocking and handling sensation (soft feel). The wax mixtures generally comprise powder mixtures and/or melt mixtures.

EXAMPLES

TABLE 1 Characterization of the ingredients of the wax mixtures used Dropping Wax type Acid number point Viscosity Metallocene PE 0 mg KOH/g 124° C. 250 mPas (140° C.) wax Metallocene PP 0 mg KOH/g 135° C. 40 mPas (170° C.) wax Oxidized 20 mg KOH/g 114° C. 200 mPas (120° C.) metallocene PE wax PE wax 0 mg KOH/g 125° C. 300 mPas (140° C.) PP wax 0 mg KOH/g  160° C.* 1500 mPas (170° C.) Oxidized PE wax 20 mg KOH/g 114° C. 200 mPas (120° C.) Amide wax 6 mg KOH/g 140° C. 10 mPas (150° C.) Montan wax 1 17 mg KOH/g  82° C. 30 mPas (100° C.) Montan wax 2 14 mg KOH/g 100° C. 300 mPas (120° C.) Carnauba wax 9 mg KOH/g  82° C. 30 mPas (90° C.) FT paraffin 0 mg KOH/g 110° C. 20 mPas (120° C.) *Softening point

TABLE 2 Wax mixtures (all mixtures micronized to DV₅₀ = 8 μm) Code Ingredient 1 Ingredient 2 Ingredient 3 Proportion M1 Oxidized Carnauba wax — 1:1 metallocene PE wax M2 Metallocene PE wax Oxidized — 7:3 metallocene PE wax M3 Metallocene PE wax Amide wax — 1:1 M4 Metallocene PE wax PTFE wax — 9:1 M5 Metallocene PE wax Oxidized PTFE wax 12:7:1  metallocene PE wax M6 Metallocene PP wax Amide wax — 1:1 M7 Metallocene PP wax Amide wax — 5:1 M8 Metallocene PP wax Metallocene PE — 1:1 wax M9 Metallocene PP wax Oxidized — 1:1 metallocene PE wax  M10 Oxidized Montan wax Montan wax 2:1:1 metallocene PE wax 1 2  M11 Metallocene PE wax Oxidized Sorbitan 1:1:1 metallocene PE tristearate wax  M12 Metallocene PE wax FT paraffin — 5:1 V1 Oxidized PE wax Carnauba wax — 1:1 V2 PE wax Oxidized PE wax — 7:3 V3 PE wax Amide wax — 1:1 V4 PE wax PTFE wax — 9:1 V5 PE wax Oxidized PE wax PTFE wax 12:7:1  V6 PP wax Amide wax — 1:1 V7 PP wax Amide wax — 5:1 V8 PP wax PE wax — 1:1 V9 PP wax Oxidized PE wax — 1:1  V10 Oxidized PE wax Montan wax Montan wax 2:1:1 1 2  V11 PE wax Oxidized PE wax Sorbitan 1:1:1 tristearate  V12 PE wax FT paraffin — 5:1

Preparation of an Aqueous Wax Dispersion from a Micropowder:

1% by weight of Tylose® is stirred into 60% by weight of water and allowed to swell briefly, after which 39% by weight of micronized oxidized wax is incorporated into the Tylose solution by dispersion.

TABLE 3 Dispersing/stability of wax mixtures Wax Dispersing/stability Example 1 M1 good/very good Example 2 M2 good/very good Example 3 M9 good/very good Example 4  M10 very good/very good Example 5 V1 good/very good Example 6 V2 good/very good Example 7 V9 moderate/moderate Example 8  V10 good/very good

Incorporation of an Aqueous Wax Dispersion into an Aqueous Acrylic Varnish:

4% by weight of the wax dispersion specified in example 2 is stirred into 96% by weight of aqueous acrylic varnish (based on Mowilith® LDM 7460) and then drawn down onto a glass plate using a frame coater (60 μm wet film thickness). After drying, the gloss is measured.

TABLE 4 Gloss of the wax mixtures Dispersion from Base wax Gloss (60° angle) Acrylic varnish no wax — 120 Example 9 Example 1 M1 22 Example 10 Example 2 M2 25 Example 11 Example 3 M9 25 Example 12 Example 4  M10 20 Example 13 Example 5 V1 30 Example 14 Example 6 V2 30 Example 15 Example 7 V9 28 Example 16 Example 8  V10 25

Incorporation of Micronized Waxes into a Nitrocellulose Standard Varnish for Purposes of Matting and Slip:

2% by weight of micronized wax are incorporated by dispersion into 98% by weight of NC varnish by means of a dissolver and then drawn down onto a glass plate using a frame coater (60 μm wet film thickness). After drying, the gloss is measured.

TABLE 5 Gloss and slip of the wax mixtures Wax Gloss (60° angle) Slip Nitrocellulose varnish No wax 138 0.42 Example 17 M3 — 0.17 Example 18 M4 45 0.12 Example 19 M5 — 0.09 Example 20 M6 25 0.10 Example 21 M7 25 — Example 22 M8 30 0.25 Example 23 M9 41 0.25 Example 24  M10 30 0.15 Example 25 V3 27 0.22 Example 26 V4 50 0.15 Example 27 V5 45 0.15 Example 28 V6 30 0.17 Example 29 V7 30 0.30 Example 30 V8 40 0.30 Example 31 V9 50 0.28 Example 32  V10 35 0.22

Incorporation into a White Hybrid Powder Coating Material for the Purpose of Improving the Pencil Hardness and Abrasion Resistance:

The waxes are mixed with the individual raw materials in a high-speed mixer, and then the raw materials are extruded at 110° C. in a twin-screw laboratory extruder (PC19-25 from APV), ground to <125 μm and applied to aluminum or steel sheet. After baking (at 180° C. for 15 minutes) the coated sheets are stored in a controlled-climate chamber for 24 hours, after which the pencil hardness (according to Wolff-Wilborn) is measured and the Taber Abraser abrasion test carried out.

TABLE 6 Pencil hardness and abrasion test Wax, in each case Pencil hardness 1% based on total according to Abrasion test formula Wolff-Wilborn after 250 turns Hybrid powder No wax 2B 52 mg coating material Example 33 M2 HB 48 mg Example 34 M3 F 35 mg Example 35 M4 F 25 mg Example 36 M6 F 20 mg Example 37 M7 H 15 mg Example 38  M10 HB 25 mg Example 39 V2 B 50 mg Example 40 V3 HB 41 mg Example 41 V4 HB 42 mg Example 42 V6 B 46 mg Example 43 V7 B 38 mg Example 44  V10 HB 40 mg

Incorporation into a Blue Hybrid Powder Coating Material for the Purpose of Improving the Dispersion and Throughput:

The waxes are mixed with one another with the individual raw materials in a high-speed mixer, and then the raw materials are extruded at 110° C. in a twin-screw laboratory extruder (PC19-25 from APV), for which it is necessary to set the metering level to a power consumption of 70% on the extruder; during this procedure, the throughput is detected; the extrudate is then ground to <125 μm and applied to aluminum or steel sheet. After baking (at 180° C. for 15 minutes) the coated sheets are stored in a controlled-climate chamber for 24 hours, after which the depth of color is measured.

TABLE 7 Depth of color Wax, in each case 1% based on total % improvement formula in throughput Depth of color Hybrid powder No wax — 100% coating material Example 45 M1 18% 110% Example 46 M2 20% 105% Example 47 M3 15% 107% Example 48 M6 30% 105% Example 49 M8 25% 107% Example 50  M10 50% 120% Example 51 V1 13% 107% Example 52 V2 15% 100% Example 53 V3 10% 102% Example 54 V6 10% 100% Example 55 V8 15% 105% Example 56  V10 45% 112%

Incorporation into an Alkyd Resin Varnish for the Purpose of Assessing the Blocking Properties and the Feel:

2% by weight of micronized wax are incorporated into the alkyd resin varnish with the aid of a dissolver, after which the varnish is applied to glass (at least 2 plates in each case) with the aid of a frame coater (60 μm wet film thickness). After storage in a controlled-climate chamber for 24 hours, the feel is assessed (subjectively), after which the plates are stored in an oven at 50° C. for 24 hours. In this case the plates are placed with the coating on top of one another and are loaded with a 500 g weight. Thereafter, the blocking behavior is assessed.

TABLE 8 Assessment of the blocking behavior Assessment scheme Blocking resistance None No blocking Trace Very slight blocking evident Little When the upper board is raised, the underneath board comes with it but parts by itself after a few seconds Some When the upper board is raised, the underneath board comes with it, but has to be separated by hand without perceptible application of force Marked When the upper board is raised, the underneath board comes with it but has to be separated with some application of force. Substantial The plates have to be separated with considerable application of force.

TABLE 9 Feel characteristics of the wax mixtures Blocking Wax Feel (subjective) characteristics Alkyl resin varnish No wax Plasticky, slightly tacky Substantial Example 57 M3 Good feel, no sticking Trace Example 58 M4 Good feel, very smooth None Example 59 M6 Good feel, smooth Trace Example 60  M10 Soft, pleasant, somewhat Little smooth Example 61 V3 Good feel, very slight Little sticking Example 62 V4 Good feel, smooth Little Example 63 V6 Slightly tacky Some Example 64  V10 Pleasant Little

Incorporation into a 2K PU Varnish, Applied to Wooden Boards, and Assessment of sandability:

2 or 4% by weight of micronized wax are incorporated by dispersion into one component of a 2K polyurethane varnish system, after which the 2nd component is added and the composition is applied by brush to a wooden board in a cross pass. The board is then left to dry in a controlled-climate chamber for 24 hours. The sanding test is then carried out, in which a sheet of abrasive paper (240 grit) is stretched over a wooden block, passed over the wooden board 20× without pressure, and then the abrasion is assessed. The lower the level of coating on the abrasive paper, the better the sandability.

TABLE 10 Sandability of additived varnish Wax Sandability 2K PU varnish No wax Very poor, abrasive paper clogged after just 10 strokes Example 65 M1 Moderate, abrasive paper almost clogged Example 66 M3 Very good, no clogging observable after 20 strokes Example 67 M6 Very good, no clogging observable after 20 strokes Example 68 M7 Good, slight clogging of the abrasive paper Example 69  M10 Good, slight clogging of the abrasive paper Example 70 V1 Poor, abrasive paper clogged after 20 strokes Example 71 V3 Good, slight clogging of the abrasive paper Example 72 V6 Good, slight clogging of the abrasive paper Example 73 V7 Poor, abrasive paper clogged after 20 strokes Example 74  V10 Poor, abrasive paper clogged after 20 strokes 

What is claimed is:
 1. A method for improving the properties of a coating material comprising the step of adding to the coating material a wax mixture comprising: a) a homopolymer or copolymer of C2-C18 a-olefins, prepared by means of metallocene catalysis, and also degradation waxes produced from relatively high-chain-length polyolefins produced by means of metallocene catalysis, and, as auxiliaries, one or more other waxes selected from the group consisting of b) PE waxes, c) PTFE waxes, d) PP waxes, e) amide waxes, f) FT paraffins, g) montan waxes, h) natural waxes, i) macrocrystalline and microcrystalline paraffins, j) polar polyolefin waxes, or k) sorbitan esters, I) polyamides, m) polyolefins, n) PTFE, o) wetting agents, p) silicates.
 2. The method as claimed in claim 1, wherein ingredient a) is an oxidate of a metallocene wax.
 3. The method as claimed in claim 1, wherein ingredient a) comprises a homopolymer or copolymer of ethylene or of propylene.
 4. The method as claimed in claim 1, wherein the wax specified as ingredient a) has a melt viscosity at 140° C. of from 10 to 10 000 mPas.
 5. The method as claimed in claim 1, wherein the wax specified as ingredient a) has a density of from 0.87 to 1.03 g/cm³.
 6. The method as claimed in claim 1, wherein the wax specified as ingredient b) is a polyethylene wax not prepared by means of metallocene catalysis, having a number-average molecular weight of from 700 to 10 000 g/mol.
 7. The method as claimed in claim 1, wherein the wax specified as ingredient d) is a polypropylene wax not prepared by means of metallocene catalysis, having a number-average molecular weight of from 700 to 10 000 g/mol.
 8. The method as claimed in claim 1, wherein the wax specified as ingredient j) is a polyethylene or polypropylene wax modified by oxidation or grafting with maleic anhydride.
 9. The method of claim 1, wherein the wax mixture is in micronized form.
 10. A coating material made in accordance with the method of claim
 1. 11. A method for improving the properties of a coating material comprising the step of adding to the coating material a wax mixture of comprising: a) a homopolymer or copolymer of C₂-C₁₈ α-olefins, prepared by means of metallocene catalysis, or degradation waxes produced from relatively high-chain-length polyolefins produced by means of metallocene catalysis, and, as auxiliaries, one or more other waxes selected from the group consisting of b) PE waxes, c) PTFE waxes, d) PP waxes, e) amide waxes, f) FT paraffins, g) montan waxes, h) natural waxes, i) macrocrystalline and microcrystalline paraffins, j) polar polyolefin waxes, or k) sorbitan esters, I) polyamides, m) polyolefins, n) PTFE, o) wetting agents, p) silicates.
 12. The method of claim 11, wherein the wax mixture is in micronized form.
 13. A coating material made in accordance with the method of claim
 11. 